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WO2014188454A1 - Procédé de préparation de graphène nanoporeux et de points quantiques de graphène - Google Patents

Procédé de préparation de graphène nanoporeux et de points quantiques de graphène Download PDF

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WO2014188454A1
WO2014188454A1 PCT/IN2014/000354 IN2014000354W WO2014188454A1 WO 2014188454 A1 WO2014188454 A1 WO 2014188454A1 IN 2014000354 W IN2014000354 W IN 2014000354W WO 2014188454 A1 WO2014188454 A1 WO 2014188454A1
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graphene
pgr
gqd
gqds
quantum dots
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Sreekumar Kurungot
Thangavelu PALANISELVAM
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Council of Scientific and Industrial Research CSIR
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Priority to KR1020157035969A priority Critical patent/KR101835879B1/ko
Priority to JP2016514539A priority patent/JP6211687B2/ja
Priority to US14/893,658 priority patent/US9637388B2/en
Publication of WO2014188454A1 publication Critical patent/WO2014188454A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/06—Graphene nanoribbons
    • C01B2204/065—Graphene nanoribbons characterized by their width or by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y10S977/774—Exhibiting three-dimensional carrier confinement, e.g. quantum dots

Definitions

  • porous graphene has also gained much attention recently in the field of nano electronics as similar to Graphene.
  • the band gap of the Graphene can be tuned as similar to the band gap of Ti0 2 (3.2 eV) by making holes on Graphene.
  • the inventors group has demonstrated a versatile method for drilling nano holes on graphene assisted by pre-formed Fe 2 03 nanoparticles and conversion of the latter to Fe 3 C through carbon spillover from Graphene. Inclusion of multi carbon vacancy along the pore openings of the two dimensional Graphene could be utilized for imparting ORR activity in the system through effective nitrogen doping.
  • the method proposed by the inventor has limitations like controlling the sizes of the pores within few nanometers and maintaining the pore distribution homogeneously throughout the surface of Graphene and reducing the wastage in the process.
  • the object of the current invention is to provide a simple and scalable process to prepare the porous graphene (pGr) and graphene quantum dots (GQDs) simultaneously from graphene with no wastage of carbonaceous material.
  • the other object of the invention is to provide a process which gives the nanoporous graphene without any metal contamination and extensive damage to the graphene framework.
  • the other object is to prepare nitrogen doped porous graphene having excellent activity towards electrochemical oxygen reduction reaction (ORR).
  • the present invention provides an in-situ process for simultaneous synthesis of nanoporous graphene (pGr) and photo luminescent graphene quantum dots (GQDs) with no wastage of carbonaceous material comprising; i. dispersing graphene with 25-35 % hydrogen peroxide (H2O2) at room temperature ranging between 25-35 °C followed by increasing the temperature to 60 to 70 ° C for 24 to 72 hrs to obtain a mixture of porous graphene (pGr) and graphene quantum dots (GQDs);
  • step (iii) drying the residue as pGras obtained in step (ii) at a temperature in the range of 40°C-60°C for 1-3 h;
  • step (ii) dialysing the filtrate as obtained in step (ii) in dialysis bag for 1 - 3 days at 27 to 30° C to obtain solution of GQ.D;
  • step (iii) optionally, nitrogen doping of the porous graphene as obtained in step (iii) to obtain nitrogen doped porous graphene.
  • the average size of graphene quantum dots as obtained in step (iv) in a single layer is 3-5nm .
  • the BET surface area of pGr as obtained in step (iii) is in the range of 204 to 240 m 2 g "1 .
  • the nitrogen doping of the porous graphene surface (pGr) was carried out by, mixing of ethanolic solution of porous graphene (pGr) as obtained in step (iii) with 1 , 10 Phenanthroline mixture at 27 to 30 ° C for a period ranging between 20 -24 hrs followed by evaporating the solvent by thermal evaporation at temperature ranging between 50 to 60 ° C for a period ranging between 10-12 hrs to obtain the composite material subsequently heating at temperature ranging between 800 to 900 ° C for a period ranging between 1 -3 hrs in a furnace saturated with inert atmosphere and cooling, washing to obtain nitrogen doped porous graphene.
  • nitrogen doped porous graphene nano pores (pGr) and GQD are useful for gas separation, water desalination, for the single atom doping (Pt, Co and In), nano-electronics and energy applications such as Li-ion batteries Li-air battery, solar cells, super capacitors, gas sensors and polymer electrolyte membrane fuel cells (PEMFCs).
  • Figure 1 depicts (a-b) HRTEM images of GQD-72 in different magnifications.
  • Inset of (a) is the diffraction pattern of GQD-72 which represents the mono crysatllinity of the material.
  • Inset of (b) is the higher magnification image of GQD-72, giving the corresponding lattice fringes possessing d value of 0.24 nm.
  • (c-d) represents the HRTEM images of pGr-72 in different magnifications; well distributed nanopores and the characteristic feature of the graphene surface are clearly visible from these images.
  • Figure 2 depicts (a) UV-Vis spectra of GQD-72.
  • Figure 4 depicts (a) CV for pGr-72, NGr and NpGr-72 in 5 m V s '1 scan rate, (b) Linear sweep voltammograms of pGr-72, NGr, NpGr-72 and E-TEK recorded in 0.1 M KOH with the scan rate of 10 m V s-1 and electrode rotation rate of 1600 rpm.
  • Figure 5 depicts accelerated durability test for (a) NpGr-72 and (b) 20 wt % Pt/C (E-TEK).
  • Figure 6 depicts (a) Single cell polarization data by using NpGr-72 and NGr (b) Pt/C (E-TEK) as the cathode catalysts (loading: 2.5 mg cm-2) and FumaTech FAA as the anion exchange membrane. 40 wt.% Pt/C (E-TEK) (loading: 0.8 mg cm-2) was used as the anode catalyst. The operating temperature is 50 °C. H2 and 02 flow rates are 50 and 100 seem respectively and 100 % relative humidity was maintained for the H2 and 02 streams.
  • E-TEK Pt/C
  • Figure 7 depict Hydrogen adsorption desorption isotherms of pGr-48 and pGr-72 at 1 atm pressure and 77 K and (b) weight percentage of hydrogen uptake of pGr-48 and pGr-72 at 1 atm pressure and 77 K.
  • FIG. 8 EDAX spectra with elemental quantification of (a) NpGr-72 and (b) NGr. It depicts the higher amount of the doped nitrogen and its chemical environment of NpGr-72 has been identified by energy dispersive X-ray analysis (EDAX).
  • EDAX energy dispersive X-ray analysis
  • Figure 9 Deconvolved N1s spectra of NpGr-72 and NGr.
  • the various nitrogen moieties as designated for the samples are as follows: (a) NpGr-72: N1 (Pyridinic), N2 (Pyrrolic), N3 (Graphitic), N4 (Quaternary) and N5 (Pyridinic N+0-); (b) NGr: N1 (Pyridinic), N2 (Pyrrolic), N3 (Graphitic) and N4 (Pyridinic N+0-).
  • N1s spectra of NpGr-72 in Figure 2a show the presence of five different peaks at 398.4 (Ni), 399.4 (N 2 ), 400.3 (N 3 ), 401 .1 (N 4 ) and 402.4 eV (N 5 ) corresponding to pyridinic, pyrrolic, graphitic, quaternary nitrogens and nitrogen bound with oxygen (pyridinic N + 0 ) respectively.
  • the deconvoluted N1s spectra of NGr in Figure 9b show the presence of four different peaks at 398.5 (Ni ), 399.3 (Ni), 400.6 (N 3 ), and 402.2 (N 4 ) corresponding to pyridinic, pyrrolic, graphitic and nitrogen bound with oxygen (pyridinic N + 0 ) respectively.
  • Graphene which is a two dimensional sp 2 carbon network, due to its high carrier mobility, mechanical flexibility and chemical stability finds wide application in development of high performance in electronics and related fields.
  • edge sites are very significant in the electrocatalytic process.
  • Creation of porosity on the graphene surface is technically challengeable, especially in the context of controlling the sizes of the pores within few nanometers and maintaining the pore distribution homogeneously throughout the surface of Graphene (Gr).
  • the inventors provide herein a simple and scalable process for functionalization of graphene using a suitable oxidizing agent that meets the desired objective of the instant invention advantageously.
  • the present invention provides an in-situ synthesis of graphene quantum dots (GQDs) and porous graphene (pGr) simultaneously by simple hydrogen peroxide (H 2 0 2 ) functionalization of graphene (Gr) under ambient condition.
  • the process helps to knock out small pieces of Gr through epoxide formation, which subsequently resulted into the generation of GQD and pGr simultaneously.
  • oxidation can be carried out at ambient temperature and (ii) does not incorporate foreign elements in to the carbon surface.
  • the present invention provides a simple, scalable, in-situ process for simultaneous synthesis of well-structured nanoporous graphene (pGr) and photo luminescent graphene quantum dots (GQDs) with no wastage of carbonaceous material comprising;
  • step (ii) dialysing the filtrate obtained in step (ii) in a dialysis bag for about 3 days to obtain solution of GQD-72.
  • Gr was dispersed in H2O2 (30 %) solution and sonicated for about 10 min. at room temperature followed by increasing the temperature of the reaction mixture to 70° C and maintaining for 72 h. Subsequently, the resulting mixture was filtered by a filter paper having a pore size of 0.44 m ( ankem Chemicals) and the residue (i.e. pGr-72) was dried at a temperature in the range of 45-55°C for about 3 h and preserved for further analyses. Total yield of pGr-72 was estimated which is -70 3 ⁇ 4. The filtrate collected was allowed for dialysis in a dialysis bag for about 3 days to obtain aqueous solution of GQD-72 which was conserved for further analysis.
  • the photo luminescent (PL) quantum yield of GQD formed after 72 h of the oxidative treatment (GQD-72) was 15.8 %
  • Table 1 below provide comparative yield of GQD's with the yield of PL GQD-72 indicating the remarkable improvement in PL quantum yield by th'e process of the instant invention.
  • Table 1 Comparison table of yield of GQDs.
  • Graphene used in the process of the invention is synthesized by pyrolysis of graphene oxide (GO) in argon (Ar) atmosphere at 700-900° C for 1 -3 h.
  • GO is synthesized by improved Hummer's method. Accordingly, a mixture of potassium permanganate (KMn0 4 ) and graphite powder (6: 1 g ratio) is added slowly to the acid mixture of con. H2SO4 and H3PO4 (9:1 ratio) with mechanical stirring at 0°C and the temperature is allowed to increase to a temperature in the range of 45-55°C and maintaining for about 12-14 hrs. This is followed by adding 30% H 2 0 2 in ice water to the reaction mixture to stop the oxidation of the reaction. The mixture is further centrifuged, washed and used for further reaction.
  • Kn0 4 potassium permanganate
  • H3PO4 9:1 ratio
  • GQDs solution obtained after dialysis show uniform dispersion of quantum dots with average particle size of graphene quantum dots in a single layer is 3-5nm.
  • Figure 1a The higher magnification image (inset of Figure 1 b with d value of 0.24 nm (1120 plane of graphene) and diffraction pattern (inset of Figure 1 a) emphasizes the higher crystallinity of the GQD-72 as similar to graphene.
  • the aqueous solution of GQD-72 shows a yellow color (inset of Figure 3a) and emits a strong green luminescence under the UV light which is likely to be due to the luminescent carbon particles.
  • the photoluminescent (PL) spectra of GQD-72 (3b) show the strongest emission at 457 nm with the Stokes shift of 117 nm on an excitation wavelength of 340 nm.
  • the energy difference ( ⁇ ) between ⁇ and TT orbital which predicts the ground state multiplicity of carbene must be less than 1.5 eV for the triplet ground state.
  • the calculated ⁇ for the green luminescence is observed at 0.47 eV, which ensures that the synthesized GQD is similar to the carbene with triplet multiplicity.
  • the process of H 2 0 2 oxidative treatment results in etching of the graphene (Gr) surface resulting in increased proportion of nanopores of smaller dimensions in the system.
  • Graphene exhibits a relatively broad pore size distribution within the range of 5 to 9 nm.
  • more pores with an average size of 0.7-3 nm are also found to be present on the graphene surface, pGr-72.
  • the high surface density of the nanopores present on pGr-72 was ensured from hydrogen sorption -desorption capacity.
  • pGr-72 showed nearly two times higher storage capacity as compared to pGr-48 which ensures the better surface density of the nanopores present on pGr-72.
  • the BET surface area of pGr is 204 m 2 g '1 .
  • HRTEM images reveal the presence of nano sized pores on Gr surface while these are absent in the case of pure Gr sheets ( Figure 1e-1f ).
  • the 5 nm average sized pores are in tune with the average size of GQD-72 indicating the derivation of these GQDs from the Gr surface.
  • the pore size distribution profile of pGr-72 which augments the presence of 5 nm sized pores with uniform distribution on Gr confirms the formation of GQDs from Gr.
  • the nanopores on the graphene surface concomitantly enriches the unsaturated carbon valancies thus providing more edge sites which act as a trapping site for other heteroatom doping. This provides a convenient way to enhance the concentration of nitrogen during the doping process and also to establish greater proportions of the desired co-ordinations which are active for facilitating ORR.
  • the present invention provides a process for nitrogen doping of the porous graphene surface (pGr-72) having excellent activity towards electrochemical oxygen reduction reaction (ORR), comprising;
  • the higher amount of the doped nitrogen and its chemical environment of NpGr-72 identified by energy dispersive X-ray analysis (EDAX) show the presence of pyridinic, pyrrolic, graphitic, quaternary nitrogens and nitrogen bound with oxygen (pyridinic N + 0 ) respectively; preferably pyridinic and pyrrolic /pyridone type nitrogens doped directly at the defect sites along the pore openings contributing to enhanced ORR activity of NpGr-72.
  • EDAX energy dispersive X-ray analysis
  • NpGr-72 In order to understand the influence of surface porosity of Gr for nitrogen doping towards the establishment of efficient catalytic sites for ORR, cyclic voltammetry was carried out for NpGr-72 in 0.1 M KOH solution (saturated with Oxygen) and the performance was compared with non-porous nitrogen doped graphene (NGr), pGr- 72 and commercial 20 wt % PtC (E-TEK). Accordingly, NpGr-72 exhibited the cathode current onset at +0.02 V, which corresponds to an appreciable reduction in the overpotential by 50 and 90 mV compared to NGr and pGr respectively.
  • the pGr-72 is observed to be electrochemically more stable compared to its commercial Pt counterpart in alkaline medium upto 2500 cycles.
  • the potential cycling causes the dissolution and sintering of Pt nanoparticles in the case of E-TEK whereas degradation of active sites in NpGr-72 is less prominent due to the stable coordination of nitrogen with the graphene moiety.
  • Graphene with well distributed nano pores as produced by the current method may be used as membrane for gas separation, water desalination, for the single atom doping (Pt, Co and In), nano-electronics and energy applications such as Li- ion batteries Li-air battery, solar cells, super capacitors, gas sensors and polymer electrolyte membrane fuel cells (PEMFCs).
  • Pt, Co and In single atom doping
  • nano-electronics and energy applications such as Li- ion batteries Li-air battery, solar cells, super capacitors, gas sensors and polymer electrolyte membrane fuel cells (PEMFCs).
  • PEMFCs polymer electrolyte membrane fuel cells
  • the Gr with well distributed nano pores as produced by the current method may be used as membrane for gas separation, water desalination, for the single atom doping (Pt, Co and In), nano-etectronics and energy applications such as Li-ion batteries Li-air battery, solar cells, super capacitors, gas sensors and polymer electrolyte membrane fuel cells (PEMFCs).
  • Pt, Co and In single atom doping
  • PEMFCs polymer electrolyte membrane fuel cells
  • the mixture was subjected to centrifugation at 12000 rpm and the supernatant solution was decanted away.
  • the resulting material was subjected to the multiple washings with water, ethanol, acetone and diethyl ether and conserved for further use.
  • Graphene oxide (GO) was loaded on the alumina boat which was placed in the quartz tube. Further, the tube was kept in tubular furnace and the tube was saturated with inert atmosphere by purging Ar with the flow rate of 0.5 seem. Further, the temperature of the furnace was increased to 900 °C and the same temperature was maintained for 3 h. This was allowed to cool to room temperature after pyrolysis with Ar flow. The pyrolysed product was preserved for further studies.
  • the pyrolysed product (NpGr-72) was cooled, washed with ethanol and preserved for further studies. Yield: 90%.
  • the nitrogen doping on the final product (NpGr-72) was ensured by ED AX and XPS analysis.
  • FIG. 1 a depicts uniform dispersion of GQDs with an average size of ca 3-5 nm.
  • the diffraction pattern (inset of Figure 1a) and higher magnification image (inset of Figure 1 b with a d value of 0.24nm (1120 plane of graphene) emphasize the higher crystallinity possessed by GQD-72 which is very much similar to the parent graphene.
  • the TEM images of pGr-72, as shown in Figure 1 c-d clearly reveal the presence of nano sized pores on Gr surface which were absent in the case of pure Gr sheets ( Figure 1e-f ).
  • the 5 nm average sized pores were in well accordance with the average size of GQD-72 which highlights the derivation of these GQDs from the Gr surface.
  • FIGs 2a to c depict the optical properties of GQD-72.
  • the UV-Vis spectrum of GQD-72 in water (Figure 2a) showed two absorption bands at 300 and 340 nm ensuring the two electronic transitions occurring under the UV light.
  • the aqueous solution of GQD-72 showed a yellow color (inset of Figure 2a) and emitted a strong green luminescence under the UV light which was likely to be due to the luminescent carbon particles.
  • Figure 2b depicts the photoluminescent (PL) spectra of GQD-72.
  • the PL spectra of GQD-72 showed the strongest emission at 457 nm with the Stokes shift of 117 nm on an excitation wavelength of 340 nm.
  • the PL peak position was red shifted from the lower wavelength to higher wavelength with reduction in intensity by change in the excitation wavelength from 340 to 460 nm, elucidating the excitation dependent PL behaviour of GQD-72.
  • the photoluminecent excitation (PLE) spectrum in Figure 2c showed two sharp peaks at 301 and 340 nm as similar to the UV-Vis spectra, which further confirmed the two transitions under the UV light.
  • the UV-Vis spectra and PLE clearly reveal that the observed green luminescence was mainly due to the transitions at 300 (4.12 eV) and 340 nm (3.65 eV) i. e.
  • Gr, pGr-72 and NpGr-72 showed sharp graphitic peaks of the (002) plane centered at 2 ⁇ of 25.7° whereas GQD-72 showed a broader peak with a shift in the 2 ⁇ to 23. , indicating the reduced size of GQDs.
  • the d- spacing also increased from Gr to GQD (3.53 to 3.61 A) due to the intercalation of oxygen functional groups which results in enhanced interlayer distance.
  • a similar d-spacing shift is also expected in the case of pGr-72 due to the oxygen functionalities.
  • the relative oxygen to carbon content ratio is more in the case of GQD over pGr due to its small particle size ( ⁇ 5nm).
  • Figure 4a compares the cyclic voltammograms of NpGr-72, NGr, pGr and Gr ⁇ taken at a potential window of 0.2 to -0.6 V against Hg/HgO reference electrode at a scan rate of 5 mV s "1 .
  • the voltammograms clearly showed that the ORR activity of all the samples as indicated by the distinct onset potentials and peaks correspond to oxygen reduction current during the cathodic scan.
  • Gr showed a well resolved cathodic peak corresponding to ORR with an onset potential of -0.088 V under oxygen saturated conditions whereas pGr-72 showed the ORR with an onset potential of -0.07 V.
  • ADT accelerated durability test
  • the holes on the porous Gr are expected to provide more edge sites which are believed to act as a trapping site for other heteroatom doping as well (boron B and Phosphorous P).

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Abstract

L'invention concerne un procédé simple et facilement échelonnable de préparation de deux matériaux carbonés à valeur ajoutée potentielle à partir de graphène. L'invention concerne également la préparation simultanée de points quantiques de graphène et de graphène poreux à partir de graphène. L'invention concerne encore du graphène poreux dopé à l'azote présentant une excellente activité dans une réaction électrochimique de réduction d'oxygène.
PCT/IN2014/000354 2013-05-24 2014-05-26 Procédé de préparation de graphène nanoporeux et de points quantiques de graphène Ceased WO2014188454A1 (fr)

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KR1020157035969A KR101835879B1 (ko) 2013-05-24 2014-05-26 나노다공성 그래핀 및 그래핀 양자점을 제조하는 방법
JP2016514539A JP6211687B2 (ja) 2013-05-24 2014-05-26 ナノ多孔性グラフェンとグラフェン量子ドットを作製する方法
US14/893,658 US9637388B2 (en) 2013-05-24 2014-05-26 Process for preparation of nanoporous graphene and graphene quantum dots

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WO2019006475A1 (fr) * 2017-06-30 2019-01-03 Nano Trek Holdings, LLC Procédé de préparation d'oxyde de graphène et d'oxyde de graphène réduit
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